Ion Exchange resin transportation and storage

ABSTRACT

Methods of stabilizing virgin ion exchange resin material are provided. The methods include rinsing virgin ion exchange resin material with deoxygenated water, introducing the rinsed virgin ion exchange resin material into a liquid impermeable compartment of a gas impermeable vessel and hermetically sealing the vessel. The methods include rinsing virgin ion exchange resin material with deoxygenated water, introducing the rinsed virgin ion exchange resin material into a gas impermeable vessel, introducing an oxygen scavenging material into the gas impermeable vessel, and hermetically sealing the vessel. A method of facilitating water treatment in a site in need thereof by providing rinsed virgin ion exchange resin material in deoxygenated water positioned in a liquid impermeable compartment of a gas impermeable vessel is also provided. A vessel containing deoxygenated water and virgin ion exchange resin material and an oxygen scavenging material is also provided.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Continuation in Part of U.S. Non-Provisionalapplication Ser. No. 15/679,217 titled “ION EXCHANGE RESINTRANSPORTATION AND STORAGE,” filed on Aug. 17, 2017, which claimspriority under 35 U.S.C. § 119(e) to U.S. Provisional Application Ser.No. 62/376,129 titled “Ion Exchange Resin Transportation to the NuclearIndustry in Dedicated Stainless Steel Vessels with DeoxygenationMembrane Option” filed on Aug. 17, 2016. This application also claimspriority under 35 U.S.C. § 119(e) to U.S. Provisional Application Ser.No. 62/629,267 titled “Antioxidant Protection for Ion Exchange Resins,”filed on Feb. 12, 2018. Each of these applications is hereinincorporated by reference in its entirety for all purposes.

FIELD OF TECHNOLOGY

Aspects and embodiments disclosed herein relate to stabilization ofvirgin ion exchange resin materials. More particularly, aspects andembodiments disclosed relate to methods of reducing a rate of oxidativedegradation of virgin ion exchange resin materials. Aspects andembodiments disclosed relate to the handling, storage, andtransportation of stabilized virgin ion exchange resin materials.

SUMMARY

In accordance with an aspect, there is provided a method of stabilizingvirgin ion exchange resin material. The method may comprise rinsing thevirgin ion exchange resin material with deoxygenated water to produce arinsed virgin ion exchange resin material. The method may compriseintroducing the rinsed virgin ion exchange resin material into a liquidimpermeable compartment of a gas impermeable vessel. The method maycomprise hermetically sealing the vessel.

In accordance with certain embodiments, the method may further compriseintroducing an oxygen scavenging material into the gas impermeablevessel. The method may comprise positioning the oxygen scavengingmaterial between an exterior wall of the liquid impermeable compartmentand an interior wall of the gas impermeable vessel.

In some embodiments, the method may comprise introducing the rinsedvirgin ion exchange resin material into the gas impermeable vesselcomprising at least one of polyethylene terephthalate, stainless steel,and epoxy-lined carbon steel.

The method may comprise rinsing the virgin ion exchange resin materialwith deoxygenated water having a concentration of dissolved oxygen ofless than about 10 ppb.

The method may comprise rinsing the virgin ion exchange resin materialin the gas impermeable vessel.

In accordance with another aspect, there is provided a method ofstabilizing virgin ion exchange material. The method may compriserinsing the virgin ion exchange resin material with deoxygenated waterto produce a rinsed virgin ion exchange resin material. The method maycomprise introducing the rinsed virgin ion exchange resin material intoa gas impermeable vessel. The method may comprise introducing an oxygenscavenging material into the gas impermeable vessel, the oxygenscavenging material being positioned such that it does not come intodirect contact with moisture. The method may comprise hermeticallysealing the vessel.

In some embodiments, the method may further comprise introducing therinsed virgin ion exchange resin material into a liquid impermeablecompartment of the gas impermeable vessel. The method may comprisepositioning the oxygen scavenging material between an exterior wall ofthe liquid impermeable compartment and an interior wall of the gasimpermeable vessel.

In accordance with certain embodiments, the oxygen scavenging materialmay comprise a ferrous compound, catechol, ascorbate, ascorbic acid,sodium hydrogen carbonate, citrus extract, an oxidative enzyme, anunsaturated hydrocarbon, a polyamide, or combinations thereof.

The method may further comprise introducing an indicator of oxygencontamination. The indicator of oxygen contamination may be a visualindicator having a redox midpoint potential E⁰ between about −0.05 V andabout +0.06 V at pH 7 and 25° C.

In accordance with another aspect, there is provided a method offacilitating water treatment at a site in need thereof. The method maycomprise providing a rinsed virgin ion exchange resin material indeoxygenated water, the rinsed virgin ion exchange resin materialpositioned in a liquid impermeable compartment of a hermetically sealedgas impermeable vessel.

In some embodiments, the method may further comprise providing an oxygenscavenging material in the gas impermeable vessel, positioned such thatit does not come into direct contact with the deoxygenated water. Themethod may comprise providing the oxygen scavenging material positionedbetween an exterior wall of the liquid impermeable compartment and aninterior wall of the gas impermeable vessel. The method may compriseproviding the oxygen scavenging material selected from a ferrouscompound, catechol, ascorbate, ascorbic acid, sodium hydrogen carbonate,citrus extract, an oxidative enzyme, an unsaturated hydrocarbon, apolyamide, and combinations thereof.

In some embodiments, the method may comprise providing the deoxygenatedwater in an amount between about 40% and about 50% of the virgin ionexchange resin material.

The method may comprise providing the deoxygenated water having lessthan about 10 ppb dissolved oxygen.

In some embodiments, the method may comprise providing an indicator ofoxygen contamination in the gas impermeable vessel.

In accordance with another aspect, there is provided a hermeticallysealed vessel. The vessel may comprise virgin ion exchange resinmaterial in deoxygenated water having less than about 10 ppb dissolvedoxygen. The vessel may also comprise an oxygen scavenging material.

In some embodiments, the virgin ion exchange resin material in thedeoxygenated water may be positioned in a liquid impermeable compartmentof the hermetically sealed vessel.

The oxygen scavenging material may be positioned between an exteriorwall of the liquid impermeable compartment and an interior wall of thevessel. The oxygen scavenging material may comprise a ferrous compound,catechol, ascorbate, ascorbic acid, sodium hydrogen carbonate, citrusextract, an oxidative enzyme, an unsaturated hydrocarbon, a polyamide,and combinations thereof.

The vessel may be constructed from a material comprising at least one ofpolyethylene terephthalate, stainless steel, and epoxy-lined carbonsteel.

The vessel may further comprise an indicator of oxygen contamination.The indicator of oxygen contamination may comprise a visual indicatorhaving a redox midpoint potential E⁰ between about −0.05 V and +0.06 Vat pH 7 and 25° C.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings are not intended to be drawn to scale. In thedrawings, each identical or nearly identical component that isillustrated in various figures is represented by a like numeral. Forpurposes of clarity, not every component may be labeled in everydrawing. In the drawings:

FIG. 1 is a schematic drawing of a vessel, according to an embodimentdisclosed herein;

FIG. 2 is a schematic drawing of a system comprising a vessel, accordingto an embodiment disclosed herein; and

FIG. 3 is a schematic drawing of a vessel, according to an embodimentdisclosed herein.

DETAILED DESCRIPTION

Ion exchange resins may generally be employed to separate componentscontained in liquid mixtures. Conventional ion exchange resins may beprepared by functionalizing a copolymer matrix with groups havingcationic and anionic sites. The anions or cations may be capable ofbeing exchanged for, or associated with, ions or molecules in the liquidhaving the same charge when the resin is in contact with the liquidmixture. The ions are exchanged stoichiometrically, maintainingelectroneutrality of the system. A resin that exchanges one positive ion(or a proportionate quantity based on valency), such as hydrogen, foranother positive ion, such as copper, iron, or sodium, is a cationresin. A resin that exchanges one negative ion (or a proportionatequantity based on valency), such as hydroxide, for another negative ion,such as chloride, sulfate, or chromate, is an anion resin. In manycases, both types of resins are used to remove various salts, such assodium chloride or calcium sulfate, from solution. A mixed bed ionexchange resin includes a combination of cation resin and anion resin toprovide a higher purity of treated water. The resin may be used until itbecomes saturated with the ions being removed. Many resins may also beregenerated and reused. For example, resins used in water treatment maybe regenerated by using strong acids (for cation resins) or strong bases(for anion resins).

Ion exchange is often used in water treatment, where ions in aqueoussolution typically displace hydrogen (H⁺) or hydroxide (OH⁻) ions boundto a substrate, for example, an ion exchange resin. This is sometimesknown as “water demineralization” or “water deionization.” Ion exchangeresins may generally be used in the fields of, for example, waterpurification, nuclear power generation, microelectronics manufacturing,semiconductor manufacturing, food processing, pharmaceuticalmanufacturing, chemical processing, and metal extraction.

Under certain conditions, ion exchange resins may experience oxidativedegradation of the copolymer matrix over an extended period of time.Liquid mixtures that are placed in contact with the resin, for example,during purification of the liquid mixture, may contain quantities ofoxidizing species such as molecular oxygen, dissolved oxygen, dissolvedchlorine, or may have an elevated temperature. Each of these may promoteundesired degradation of the copolymer matrix. In some instances, ionexchange resins may experience oxidative degradation during handling,storage, or transportation prior to use. For example, water or air thatis in contact with ion exchange resins prior to use may also promotedegradation of the copolymer matrix.

Specifically, it is believed that during oxidative degradation,carbon-carbon bonds rupture, breaking cross-links between individualpolymer chains and/or links between individual styrene moieties. As usedherein, “oxidative degradation” of an ion exchange resin material refersto the loss of carbon-carbon bonds of the cross-links between individualpolymer chains or styrene moieties of the material's copolymer matrix.While not wishing to be bound by any particular theory, it is believedthat the loss of such bonds may cause an increase in water retentioncapacity and, ultimately, in the release of organic contaminants, suchas segments of functionalized linear polystyrene. Oxidative degradationof the copolymer matrix may be undesirable for commercial operation ofan ion exchange or chromatographic process. For example, resins whichlose cross-links may become relatively soft and swell to a greaterextent. Resin softness and increased swelling as a result of oxidativedegradation may ultimately cause one or more of an increased bedpressure drop, a reduced flow rate for the liquid mixture being treated,and a reduced operating capacity for removing chemical species fromliquids to be treated.

Additionally, the loss of cross-links in the copolymer matrix mayincrease the release of organic contaminants into column effluent whichcan be unacceptable in some applications, such as in the nuclear powergeneration industry. Organic contaminants, for example, from degradedion exchange resin, may create a source of potential corrosion toprocess equipment or foul other ion exchange resins associated with aprocess. Ionic contaminants can also arise from degraded ion exchangeresin. For instance, in an exemplary treatment process, cation exchangeresin may contain a fixed sulfonic acid charge on a styrene backbone.The sulfonic acid is negatively charged. A positively charged ion, suchas sodium or calcium, can be exchanged with another ion from the ionexchange resin, for example a hydrogen ion (H+), such that the sodium orcalcium is removed from the liquid being treated. However, in someinstances, the resin can degrade to an extent that sulfate ions leachfrom the cation exchange resin. The leaching sulfate ions can have adetrimental effect on the quality of the treated water.

Previously, those in industry attempted to remedy oxidative degradationof ion exchange resin and its associated problems by increasing theamount of cross-linking monomer used in preparing the copolymer matrix.However, an increase in the number of cross-links generally rendered theresulting resin bead less compatible with liquid mixtures, therebyresulting in reduced diffusion into the bead and poor operatingcapacity. A highly cross-linked resin may also exhibit poor regenerationefficiency and may be impermeable with respect to large molecules, suchas glucose, fructose, and other sugars. Furthermore, increasing thecross-link density may not address problems associated with release oforganic contaminants, since degradation still occurs.

Others in industry attempted to remedy oxidative degradation of ionexchange resin by substituting a halogen for a hydrogen at a tertiarycarbon adjacent to a benzene ring of a styrene moiety. Briefly, aspostulated in U.S. Pat. No. 3,342,755, incorporated herein by referencein its entirety for all purposes, a possible mechanism for degradationof the copolymer matrix is related to a “weak link” identified at atertiary carbon adjacent to the benzene ring of a styrene moiety. Thetertiary carbon is deemed a weak link due to the tendency of itsattached hydrogen to form hydroperoxide with oxidizing agents likemolecular oxygen or chlorine. The hydroperoxides may eventually lead tosplitting of carbon chains associated with the copolymer. In the '755patent, the inventors attempted to remedy the degradation by employing amonomer such as ortho-chlorostyrene, that does not contribute to resinstability.

When degradation of ion exchange resin does occur, conventionally, anattempt may be made to rinse degradation products from the ion exchangeresin unless resin performance has been compromised. When rinsed withstandard rinse water (non-deoxygenated water) the ion exchange resin maycontinue to experience oxidative degradation and/or contamination.Residual polymer fragments and impurities during polymerization andactivation steps in the manufacturing of ion exchange resin areentangled and will slowly leach from the resins. These also must berinsed out to an acceptable level in certain industrial applications.Furthermore, in certain instances, rinsing the ion exchange resingenerates a large volume of waste. For example, in the nuclear industry,rinsing the ion exchange resin may generate a large volume orradioactive waste water that is complicated to dispose of There exists aneed for stabilization of virgin ion exchange resin while it remainsoffline, prior to use.

Ion exchange resin may be stabilized, and oxidative degradation of theion exchange resin may be prevented by limiting exposure of the resin tooxidants such as molecular oxygen, dissolved oxygen, or chlorine.Conventionally, before being used to treat a liquid, ion exchange resinsare often stored in vessels comprising moisture. The present inventorsrecognized that ion exchange resin may be stabilized prior to use bypreventing exposure of the ion exchange resin to oxygen and/or chlorinedissolved in the standard rinse water and limiting a rate of oxidativedegradation of the resin. Furthermore, conventional ion exchange resinstorage vessels may generally allow ingress of air into the vessel,causing a rapid rate of oxidative degradation of the ion exchange resin.The present inventors have recognized that ion exchange resin mayfurther be stabilized by preventing contact with oxygen, for example,from ambient air, further limiting oxidative degradation of the ionexchange resin. Stabilization may allow the ion exchange resin to remainviable while offline for a predetermined period of time as compared toion exchange resin that is conventionally stored prior to use. Methodsdisclosed herein may also reduce a volume of waste water that isgenerated during rinsing.

Aspects and embodiments disclosed herein relate to stabilization ofvirgin ion exchange resin material. In some embodiments, stabilizationof the ion exchange resin may refer to maintaining stability of the ionexchange resin over time, for example during handling, storage, and/ortransportation. Stabilization and maintained stability may relate to areduction in the rate of oxidative degradation of the virgin ionexchange resin material. Specifically, as used herein, “stabilized” ionexchange resin material may refer to ion exchange resin material havinga reduced rate of oxidative degradation over a predetermined period oftime.

Systems and methods of stabilizing virgin ion exchange resin materialare disclosed. Methods of stabilizing ion exchange resin may compriserinsing virgin ion exchange resin material with deoxygenated water toproduce a rinsed virgin ion exchange resin material. Methods ofstabilizing ion exchange resin may comprise introducing the rinsedvirgin ion exchange resin material into a gas impermeable vessel.Methods of stabilizing virgin ion exchange resin material may comprisehermetically sealing the gas impermeable vessel.

In some embodiments, methods of stabilizing ion exchange resin maycomprise rinsing virgin ion exchange resin material with deoxygenatedwater having a concentration of dissolved oxygen of less than about 10ppb. Methods of stabilizing ion exchange resin may comprise rinsingvirgin ion exchange resin material with deoxygenated water having aconcentration of dissolved oxygen of about 1 ppb. Methods of stabilizingion exchange resin may comprise rinsing virgin ion exchange resinmaterial with deoxygenated water having a concentration of chlorine ofless than about 10 ppb. Methods of stabilizing ion exchange resin maycomprise rinsing virgin ion exchange resin material with deoxygenatedwater having a concentration of chlorine of about 1 ppb.

In certain embodiments, methods disclosed herein may comprise rinsingvirgin ion exchange resin material by introducing deoxygenated waterinto the gas impermeable vessel with the virgin ion exchange resinmaterial, and removing interstitial deoxygenated water from the vessel.Rinsing with non-deoxygenated deionized water may be an improvement overnot rinsing immediately prior to usage of water at customer sites. Apre-rinse may be designed to remove residual polymers and organiccompound fragments entangled in resins. The deoxygenation of deionizedwater may minimize the incidence of oxygen in deionized rinse waterbreaking down the resin itself, which may generally contribute to theorganic (as measured by Total Organic Carbon—TOC) impurity level comingfrom ion exchange resins.

In some embodiments, methods disclosed herein may comprise maintaining amoisture content in the rinsed virgin ion exchange resin material.Maintaining a moisture content may be related to polymer cross-linkagerequired for resin function, minimizing leaching of organic compounds,and increasing physical strength. For instance, in some embodiments,methods may comprise maintaining at least about 40% moisture content inthe rinsed virgin ion exchange resin material. In some embodiments,methods may comprise maintaining about 50% moisture content in therinsed virgin ion exchange resin material. In some embodiments, methodsmay comprise maintaining between about 40% and about 50% moisturecontent in the rinsed virgin ion exchange resin material.

In accordance with certain embodiments, methods disclosed herein mayfurther comprise producing deoxygenated water. For instance, thedeoxygenated water may be produced by deoxygenating non-deoxygenatedwater. The non-deoxygenated water may be deoxygenated by treating toremove dissolved oxygen. In some embodiments, the non-deoxygenated watermay be deoxygenated by passing through a deoxygenation membrane. In someembodiments, the non-deoxygenated water may be deoxygenated bysubjecting non-deoxygenated water to vacuum degasification.

In some embodiments, methods disclosed herein may comprise rinsing thevirgin ion exchange resin material with deoxygenated water having aconcentration of dissolved oxygen effective to reduce a rate ofoxidative degradation of the virgin ion exchange resin material. Forinstance, the rate of oxidative degradation may be reduced such that afirst volume of water treated by the virgin ion exchange resin materialcomprises less than about 10 ppb total organic carbon. In someembodiments, the rate of oxidative degradation may be reduced such thatthe first volume of water treated by the virgin ion exchange resinmaterial comprises less than about 10 ppb total organic carbon aftermaintaining the virgin ion exchange resin material in the vessel for apredetermined period of time.

In some embodiments, the rate of oxidative degradation may be reducedsuch that a first volume of water treated by the virgin ion exchangeresin material comprises less than about 10 ppb sulfate. In someembodiments, the rate of oxidative degradation may be reduced such thata first volume of water treated by the virgin ion exchange resinmaterial comprises less than about 10 ppb chloride. The rate ofoxidative degradation may be reduced such that the first volume of watertreated by the virgin ion exchange resin material comprises less thanabout 10 ppb sulfate and/or less than about 10 ppb chloride aftermaintaining the virgin ion exchange resin material in the vessel for apredetermined period of time. Organically bound chloride and sulfatesare typically measured collectively as TOC. Individual organic sulfatesand organic chlorides in virgin untreated resin may break down to formionic chlorides and sulfates. These compounds may be measuredanalytically by UV light, which breaks down the organic compound,leaving ionic chlorides and sulfates which may be analyzed usingtraditional methods.

In some embodiments, the rate of oxidative degradation may be reducedsuch that the first volume of water treated by the virgin ion exchangeresin material comprises less than about 10 ppb total organic carbon,less than about 10 ppb sulfate, and/or less than about 10 ppb chlorideafter maintaining the virgin ion exchange resin material in the vesselfor at least about six months.

In some embodiments, methods disclosed herein may further compriseunsealing the vessel and rinsing the virgin ion exchange resin material.The method may further comprise unsealing the vessel and rinsing thevirgin ion exchange resin material after maintaining the virgin ionexchange resin material in the vessel for a predetermined period oftime. For instance, the method may further comprise unsealing the vesseland rinsing the virgin ion exchange resin material after maintaining thevirgin ion exchange resin material in the vessel for at least about sixmonths. The method may further comprise unsealing the vessel and rinsingthe virgin ion exchange resin material with deoxygenated water and/ordeionized water (deoxygenated or non-deoxygenated) prior to use.

In accordance with another aspect, there are provided methods offacilitating water treatment at a site in need thereof. The methods offacilitating water treatment at a site may comprise rinsing virgin ionexchange resin material with deoxygenated water to produce a rinsedvirgin ion exchange resin material. The methods of facilitating watertreatment may comprise introducing the rinsed virgin ion exchange resinmaterial into a gas impermeable vessel. The methods may comprisehermetically sealing the vessel. In some embodiments, the methods maycomprise providing the gas impermeable vessel comprising the rinsedvirgin ion exchange resin material and residual moisture to the site,for example, to the water treatment site. The residual moisture contentmay comprise, for example, between about 40% and about 50% moisturecontent.

In some embodiments, methods of facilitating water treatment at a sitein need thereof may comprise rinsing virgin ion exchange resin materialwith deoxygenated water having a concentration of dissolved oxygen ofless than about 10 ppb. The methods of facilitating water treatment maycomprise rinsing virgin ion exchange resin material with deoxygenatedwater having a concentration of dissolved oxygen of about 1 ppb. Themethods of facilitating water treatment may comprise rinsing virgin ionexchange resin material with deoxygenated water having a concentrationof chlorine of less than about 10 ppb. The methods of facilitating watertreatment may comprise rinsing virgin ion exchange resin material withdeoxygenated water having a concentration of chlorine of about 1 ppb.

In accordance with certain embodiments, methods disclosed herein mayfurther comprise providing instructions. Methods may comprise providinginstructions to maintain the virgin ion exchange resin material in thehermetically sealed vessel for a predetermined period of time. Forexample, methods may comprise providing instructions to maintain thevirgin ion exchange resin material in the hermetically sealed vesseluntil it is ready to be used. In some embodiments, methods may furthercomprise providing instructions to unseal the vessel and rinse thevirgin ion exchange resin material with deoxygenated water, for example,prior to use. Methods may comprise providing instructions to unseal thevessel and rinse the virgin ion exchange resin material prior to use in,for example, water treatment.

In accordance with another aspect, there is provided a vessel comprisingvirgin ion exchange resin material and deoxygenated water. In someembodiments, the vessel may be hermetically sealed. In some embodiments,the vessel may comprise deoxygenated water having less than about 10 ppbdissolved oxygen. The vessel may comprise deoxygenated water having lessthan about 10 ppb chlorine.

In some embodiments, the vessel may comprise a packaged desiccant media.For example, the vessel may comprise a packaged desiccant media withinthe vessel. In some embodiments, the vessel may be constructed from agas impermeable material. For instance, the vessel may be constructedfrom at least one of stainless steel and epoxy-lined carbon steel.

In some embodiments, the virgin ion exchange resin material may becation exchange resin. In some embodiments, the virgin ion exchangeresin material may be anion exchange resin or mixed cation exchangeresin and anion exchange resin.

In accordance with an aspect, there is provided a method of stabilizingvirgin ion exchange resin material. The method comprises rinsing thevirgin ion exchange resin material with deoxygenated water to produce arinsed virgin ion exchange resin material. The method may furthercomprise introducing the rinsed virgin ion exchange resin material intoa gas impermeable vessel. The method may comprise introducing the rinsedvirgin ion exchange resin material into a designated compartment of thevessel, for example, into a liquid impermeable compartment. The methodmay comprise introducing a preservative, an oxygen scavenging material,and/or an indicator of oxygen contamination into the gas impermeablevessel. The method may further comprise hermetically sealing the vessel.The method may further comprise purging the gas impermeable vessel ofoxygen. In certain embodiments, the method may comprise removing thepreservative, oxygen scavenging material, and indicator of oxygencontamination prior to use of the ion exchange resin.

As used herein, “virgin” ion exchange resin material may refer to unusedor unspent ion exchange resin material. Virgin ion exchange resinmaterial may include newly manufactured resin and/or used resin that hasbeen processed to meet required specifications for new use. Forinstance, raw or unrefined resin may be processed for new use bytreating with high purity water. Used resin may also be regenerated forreuse by treating with strong acids or strong bases. Virgin ion exchangeresin material may include cation exchange resin, anion exchange resin,and mixed cation exchange resin and anion exchange resin.

Embodiments disclosed herein may incorporate rinsing ion exchange resinmaterial with deoxygenated water. Deoxygenated water is water that hasbeen treated for removal of molecular oxygen, for example, of dissolvedoxygen. Generally, non-deoxygenated water may comprise more than about 1ppm molecular dissolved oxygen, and up to about 20 ppm dissolved oxygenor more. Dissolved oxygen in water may fluctuate with temperature,salinity, pH, conductivity, dissolved solids concentration, and pressurechange. Dissolved oxygen concentration may be measured by one or more ofmeter, sensor, Winkler titration, and a colorimetric method. Embodimentsdisclosed herein may incorporate measuring one or more of temperature,pressure, salinity, pH, conductivity, total dissolved solids (TDS)concentration, and dissolved oxygen concentration of water.

In accordance with certain embodiments, methods disclosed herein mayfurther comprise producing deoxygenated water. Deoxygenated water may beproduced by deoxygenating non-deoxygenated water, for example, from asource of non-deoxygenated water. Deoxygenated water may be produced bytreating non-deoxygenated water to remove dissolved oxygen. In someembodiments, deoxygenating non-deoxygenated water may remove at leastabout 75% of dissolved oxygen. Deoxygenating non-deoxygenated water mayremove at least about 75%, at least about 80%, at least about 85%, atleast about 90%, at least about 95%, at least about 99%, or about 100%of dissolved oxygen from the non-deoxygenated water. Deoxygenatingnon-deoxygenated water may remove between about 90% and about 100% ofdissolved oxygen from non-deoxygenated water. Non-deoxygenated water maycomprise deionized water, ultrapure water, high purity water, distilledwater, microfiltered water, ultrafiltered water, water that has beensubjected to reverse osmosis or ultraviolet oxidation, granularactivated carbon treated water, or water that has otherwise beenprocessed to remove contaminants.

Non-deoxygenated water may be deoxygenated by passing through adeoxygenation membrane. For instance, the deoxygenation membrane maycomprise a Liqui-Cel® membrane contactor (manufactured by 3M IndustrialGroup, Maplewood, Minn.). Briefly, a deoxygenation membrane may removedissolved gases from liquids with a mass transfer driving force.According to Henry's law, the amount of gas dissolved in a liquid atequilibrium is proportional to the gas's partial pressure in thevapor-phase in contact with the liquid. Under standard temperature andpressure (25° C. and 1 atm), at equilibrium water may comprise about 8.5ppm dissolved oxygen, 14.5 ppm dissolved nitrogen, and some dissolvedcarbon dioxide. By reducing the partial pressure of a gas in contactwith the liquid, the amount of gas dissolved in the liquid may bereduced correspondingly. The partial pressure of the gas may be reducedby lowering the total pressure of the gas phase or altering theconcentration of the gases in the gas phase. Each of these changes maybe applied to the gas side of the membrane, driving out dissolved gasesfrom the liquid through the membrane.

Non-deoxygenated water may be deoxygenated by subjecting to vacuumdegasification. Vacuum degasification may be achieved with a vacuumdegasification tower or specialized vacuum chamber. To reduce aconcentration of gas dissolved in a liquid with vacuum degasification,the total pressure of the gas phase may be lowered by applying a vacuumto the gas. Mass transfer may drive out dissolved gases from a liquid incontact with the gas.

Non-deoxygenated water may be deoxygenated by subjecting it to an oxygenscavenging resin. The oxygen scavenging resin may be included in acolumn or other device. In some embodiments, the oxygen scavenging resinmay include a catalyst. The catalyst may include a metal halide. In someembodiments, the catalyst may include sodium chloride. The catalyst mayinclude palladium or a palladium compound, for example, palladiumchloride.

In some embodiments, methods disclosed herein comprise rinsing thevirgin ion exchange resin material with deoxygenated water having aconcentration of dissolved oxygen effective to reduce a rate ofoxidative degradation of the virgin ion exchange resin material.Generally, a reduced rate of oxidative degradation may contribute toresin stability, capacity for purifying liquids, reduced rate ofcross-linkage break down, reduced incidence of impurities, improved beadintegrity, and/or reduced concentration of ionic contaminants in treatedliquid. For instance, in some embodiments, a stabilized ion exchangeresin may have between about a 90% and about a 70% reduced rate ofcross-linkage break down over a predetermined storage period, forexample, a storage period of at least six months. A stabilized ionexchange resin may have about a 100% reduced rate of cross-linkage breakdown, about a 90% reduced rate of cross-linkage break down, about an 80%reduced rate of cross-linkage break down, about a 70% reduced rate ofcross-linkage break down, or about a 60% reduced rate of cross-linkagebreak down. The % reduction in degradation (and de-cross-linkage) may beis dependent on the concentration of oxidizer present as well as ironand other metals in or on the resin which serve as a catalyst forbreakdown.

In some embodiments, a stabilized ion exchange resin may comprise lessthan about 100 ppm metallic impurities (dry wt.), including, forexample, aluminum, copper, iron, sodium, and lead, and/or less thanabout 10 ppm organic impurities (soak), including, for example, totalorganic carbon (TOC), sulfate, and chloride, after a predeterminedstorage period, for example, a storage period of at least six months.Specifically, a stabilized ion exchange resin may comprise less than orequal to about 50 ppm iron impurities, less than or equal to about 40ppm, less than or equal to about 30 ppm, less than or equal to about 20ppm, less than or equal to about 10 ppm, less than or equal to about 5ppm, or less than or equal to about 1 ppm iron impurities. A stabilizedion exchange resin may comprise less than or equal to about 5 ppm TOC,sulfate, or chloride impurities, less than about 4 ppm, less than about3 ppm, less than about 2 ppm, less than about 1 ppm, less than about 0.5ppm, or less than about 0.1 ppm TOC, sulfate, or chloride impurities,less than about 1 ppb of TOC, and even less than about 0.5 ppb of TOC.These concentrations may be measured analytically, in the rinse waterpassing through the resin and/or soaking of the resin and measuring theTOC in the effluent water. Levels are being measured to less than 1 ppband even less than 0.5 ppb of TOC. In some embodiments, a stabilized ionexchange resin material that has been stored for a predetermined storageperiod may substantially resemble, for example in bead integrity,concentration of impurities, and/or concentration of ionic contaminantsin treated liquid, a new or regenerated ion exchange resin material.

Methods disclosed herein may involve a predetermined storage period. Thepredetermined storage period may generally include any time the ionexchange resin is kept in the hermetically sealed vessel. The storageperiod may include storage, handling, transportation, or any purpose formaintaining the ion exchange resin within the hermetically sealedvessel. As used herein, a predetermined storage period may include astorage period of at least about 15 days, a storage period of at leastabout 30 days, a storage period of at least about one month, a storageperiod of at least about two months, a storage period of at least aboutthree months, a storage period of at least about six months, a storageperiod of at least about nine months, a storage period of at least about12 months, a storage period of at least about 18 months, or a storageperiod of at least about 24 months.

In some embodiments, the rate of oxidative degradation of a virgin ionexchange resin material may be reduced such that a first volume of watertreated by the virgin ion exchange resin material comprises less thanabout 1 ppb TOC to less than about 10 ppb TOC. In some embodiments, therate of oxidative degradation may be reduced such that the first volumeof water treated by the virgin ion exchange resin material comprisesless than about 1 ppb TOC to less than about 10 ppb TOC aftermaintaining the virgin ion exchange resin material in the vessel for apredetermined period of time. For instance, the first volume of watertreated may comprise less than about 30 ppb TOC, less than about 20 ppbTOC, less than about 10 ppb TOC, less than about 5 ppb TOC, less thanabout 1 ppb TOC, less than about 0.5 ppb TOC, or less than about 0.1 ppbTOC.

As disclosed herein, a first volume of water treated by ion exchangeresin material includes an initial monitored soak or rinse of an ionexchange resin material, once the ion exchange resin material is placedon line to treat water. In some embodiments, the concentration ofcontaminants in the first volume of water treated may be measured fromwater that is in contact with the ion exchange resin material. In otherembodiments, the concentration of contaminants in the first volume ofwater treated may be measured downstream from the ion exchange resinmaterial contact, for example such that the water is diluted orconcentrated in downstream processes. In some embodiments, the water maybe diluted or concentrated at least about 100, about 200, or about 300times. In such embodiments, the concentration of contaminants measuredin the diluted or concentrated water may be extrapolated to determinethe concentration of contaminants in non-diluted or non-concentratedfirst volume of treated water. Accordingly, a concentration ofcontaminants in the first volume of treated water, as disclosed herein,may refer to a non-diluted and non-concentrated concentration ofcontaminants. The first volume of treated water may comprise, forexample, between about 25 gallons and about 150 gallons of treatedwater. In some embodiments, the non-diluted, non-concentrated firstvolume of treated water comprises about 25 gallons, about 50 gallons,about 75 gallons, about 100 gallons, about 125 gallons, or about 150gallons of treated water. Alternatively, the first 15-20 resin bedvolumes of rinse water passed through the ion exchange resin materialmay contain high ppb or low ppm levels of organics, including organicsulfates and organic chlorides.

In some embodiments, the rate of oxidative degradation may be reducedsuch that a first volume of water treated by the virgin ion exchangeresin material comprises less than about 10 ppb sulfate. The rate ofdegradation while in service may be impacted by temperature, nuclearradiation, and/or oxidation and metals present on the resin. In someembodiments, the rate of oxidative degradation may be reduced such thata first volume of water treated by the virgin ion exchange resinmaterial comprises less than about 10 ppb chloride. The rate ofoxidative degradation may be reduced such that the first volume of watertreated by the virgin ion exchange resin material comprises less thanabout 10 ppb sulfate and/or less than about 10 ppb chloride aftermaintaining the virgin ion exchange resin material in the vessel for apredetermined period of time. For instance, the first volume of watertreated may comprise less than about 30 ppb sulfate or chloride, lessthan about 20 ppb sulfate or chloride, less than about 10 ppb sulfate orchloride, less than about 5 ppb sulfate or chloride, less than about 1ppb sulfate or chloride, less than about 0.5 ppb sulfate or chloride, orless than about 0.1 ppb sulfate or chloride.

In some embodiments, the rate of oxidative degradation may be reducedsuch that the first volume of water treated by the virgin ion exchangeresin material comprises less than about 10 ppb TOC, less than about 10ppb sulfate, and/or less than about 10 ppb chloride after maintainingthe virgin ion exchange resin material in the vessel for a predeterminedstorage period, for example at least about six months.

In some embodiments, the deoxygenated water may comprise less than about0.1 ppm dissolved oxygen. For instance, deoxygenated water may compriseless than about 0.1 ppm, less than about 50 ppb, less than about 40 ppb,less than about 30 ppb, less than about 20 ppb, less than about 10 ppb,less than about 8 ppb, less than about 6 ppb, less than about 5 ppb,less than about 4 ppb, less than about 3 ppb, less than about 2 ppb,less than about 1 ppb, or less than about 0.5 ppb dissolved oxygen.

Deoxygenation may remove other dissolved gases in the water, forexample, dissolved carbon dioxide, dissolved nitrogen, and other ambientair gases. In some embodiments, the deoxygenated water may comprise lessthan about 0.1 ppm dissolved carbon dioxide or dissolved nitrogen. Forinstance, deoxygenated water may comprise less than about 0.1 ppm, lessthan about 50 ppb, less than about 40 ppb, less than about 30 ppb, lessthan about 20 ppb, less than about 10 ppb, less than about 8 ppb, lessthan about 6 ppb, less than about 5 ppb, less than about 4 ppb, lessthan about 3 ppb, less than about 2 ppb, less than about 1 ppb, or lessthan about 0.5 ppb dissolved carbon dioxide or dissolved nitrogen.

Methods disclosed herein may comprise treating deoxygenated water ornon-deoxygenated water to remove oxidizing contaminants. Deoxygenated ornon-deoxygenated water may comprise low quantities of other oxidizingcontaminants, for example chlorine chloramine, and/or hydrogen peroxide.Deoxygenated or non-deoxygenated water may be treated with membranefiltration, reverse osmosis, high purity reducing agents (for example,sodium bisulfite) or granulated active carbon to remove oxidizingcontaminants like chlorine. In some embodiments, deoxygenated ornon-deoxygenated water may comprise less than about 0.1 ppm chlorine.For instance, deoxygenated water may comprise less than about 0.1 ppm,less than about 50 ppb, less than about 40 ppb, less than about 30 ppb,less than about 20 ppb, less than about 10 ppb, less than about 8 ppb,less than about 6 ppb, less than about 5 ppb, less than about 4 ppb,less than about 3 ppb, less than about 2 ppb, less than about 1 ppb, orless than about 0.5 ppb chlorine, chloramine, and hydrogen peroxide.

Methods disclosed herein may comprise rinsing virgin ion exchange resinmaterial by introducing deoxygenated water into the gas impermeablevessel with the virgin ion exchange resin material, and removinginterstitial (oxygenated) water from the vessel. For instance, thevessel comprising virgin ion exchange resin material may be filled withdeoxygenated water and substantially drained of the deoxygenated water,displacing the oxygenated water with deoxygenated water. In someembodiments, methods disclosed herein may comprise maintaining amoisture content in the rinsed virgin ion exchange resin material. Asdisclosed herein, moisture content may refer to the quantity of liquidor water contained in a material. Moisture content may be defined as theratio of mass of liquid, for example water, in a sample to the mass ofsolids, for example, ion exchange resin, in the sample expressed as apercentage. The interstitial moisture is the water in the void spacebetween individual resin beads. The moisture of the bead itself is themoisture or hydration within the resin bead that is measured for %moisture. Most plastics (and other materials) have an inherent amount ofmoisture within the material that can be dried and the difference inweight is measured. The deoxygenation portion of methods disclosedherein is displacing, and otherwise removing, both locations ofoxygenated water.

In some embodiments the method comprises maintaining at least about 20%moisture content in the rinsed virgin ion exchange resin material.Methods may comprise maintaining at least about 20%, at least about 30%,at least about 40%, at least about 50%, at least about 60%, or at leastabout 70% moisture content in the rinsed ion exchange resin material. Insome embodiments, the method comprises maintaining less than about 50%moisture content in the rinsed virgin ion exchange resin material. Themethod may comprise maintaining less than about 80%, less than about70%, less than about 60%, less than about 50%, less than about 40%, orless than about 30% moisture content in the rinsed ion exchange resinmaterial. In some embodiments, the method comprises maintaining betweenabout 20% and about 80%, between about 30% and about 60%, or betweenabout 40% and about 50% moisture content in the rinsed virgin ionexchange resin material. The residual moisture content may be maintainedin the virgin ion exchange resin material while the vessel is sealed,for example, while the vessel comprising rinsed virgin ion exchangeresin material is handled, stored, or transported. In some embodiments,the moisture content may contribute to stabilization of the rinsedvirgin ion exchange resin material over time. For instance, the moisturecontent may contribute to a reduced rate of oxidative degradation of thevirgin ion exchange resin material.

Higher cross-linkage resins may guard against the significance ofoxidative degradation. The higher cross-linkage contains entangledorganics resulting in some period of lower TOC levels. This effect maybe nullified with continued oxidizer exposure to the resin.

In some embodiments, methods disclosed herein may further compriseunsealing the vessel and rinsing the virgin ion exchange resin material.The method may further comprise unsealing the vessel and rinsing thevirgin ion exchange resin material after maintaining the virgin ionexchange resin material in the vessel for a predetermined period oftime, as previously described. For instance, the method may furthercomprise unsealing the vessel and rinsing the virgin ion exchange resinmaterial after maintaining the virgin ion exchange resin material in thevessel for at least about six months. The method may further compriseunsealing the vessel and rinsing the virgin ion exchange resin materialprior to use. The virgin ion exchange resin material may be rinsed priorto use with deoxygenated water. In some embodiments, the virgin ionexchange resin material may be rinsed prior to use with deoxygenatedwater having any concentration of dissolved oxygen, dissolved gases, oroxidizing contaminants as previously disclosed herein. The virgin ionexchange resin material may be rinsed prior to use with deoxygenatedwater having been produced by any of the methods previously disclosedherein.

In accordance with another aspect, there is provided a method offacilitating water treatment at a site in need thereof. The site in needthereof may be related to, for example, nuclear power generation,microelectronics manufacturing, semiconductor manufacturing, foodpreparation, pharmaceutical manufacturing, chemical processing, andmetal extraction, or any site in need of water treatment that maybenefit from ion exchange water treatment technology.

The method of facilitating water treatment at a site may compriseproviding a rinsed virgin ion exchange resin material in deoxygenatedwater, as previously described herein. The rinsed virgin ion exchangematerial may be provided in a hermetically sealed gas impermeablevessel. In some embodiments, the rinsed virgin ion exchange resinmaterial may be provided in a liquid impermeable compartment of thehermetically sealed vessel. The method may further comprise providingone or more of a preservative, an oxygen scavenging material, or anindicator of oxygen contamination within the hermetically sealed vessel.

Generally, the method of facilitating water treatment at a site maycomprise rinsing virgin ion exchange resin material with deoxygenatedwater to produce a rinsed virgin ion exchange resin material,introducing the rinsed virgin ion exchange resin material into a gasimpermeable vessel, hermetically sealing the vessel, and purging thevessel of oxygen, as previously described herein. The method offacilitating water treatment may comprise providing the gas impermeablevessel comprising the rinsed virgin ion exchange resin material andresidual moisture to the site, for example, to the water treatment site.In some embodiments, the method of facilitating water treatment mayfurther comprise providing instructions for use of the vessel comprisingvirgin ion exchange resin material.

Residual moisture content may comprise maintaining a percentage ofmoisture content in the rinsed ion exchange resin, as previouslydescribed. For example, residual moisture content may comprise betweenabout 40% and about 50% moisture content. Residual moisture content maycomprise between about 20% and about 80%, between about 30% and about60%, or between about 40% and about 50% moisture content in the rinsedvirgin ion exchange resin material, or any amount of moisture content aspreviously described.

In some embodiments, the method of facilitating water treatment at asite in need thereof may comprise rinsing virgin ion exchange resinmaterial with deoxygenated water, for example, having a concentration ofdissolved oxygen of less than about 10 ppb. In some embodiments, thevirgin ion exchange resin material may be rinsed with deoxygenated waterhaving any concentration of dissolved oxygen, dissolved gases, oroxidizing contaminants as previously disclosed herein.

In accordance with certain embodiments, methods disclosed herein mayfurther comprise providing instructions. Methods may comprise providinginstructions to maintain the virgin ion exchange resin material in thehermetically sealed vessel for a predetermined period of time. Forexample, methods may comprise providing instructions to maintain thevirgin ion exchange resin material in the hermetically sealed vesseluntil it is ready to be used. The predetermined period of time mayinclude any amount of storage, handling, and/or transportation timerequired before use of the ion exchange resin. The predetermined periodof time may include any predetermined period of time as previouslydescribed herein.

Methods disclosed herein may comprise providing instructions to maintainthe hermetically sealed vessel under certain conditions. For instance,methods may comprise providing instructions to maintain a vesselcomprising cation exchange resin at a temperature of below at leastabout 210° F. (99° C.), below at least about 200° F. (93° C.), or belowat least about 190° F. (88° C.). Methods may comprise providinginstructions to maintain a vessel comprising anion exchange resin ormixed anion and cation exchange resin at a temperature of below at leastabout 130° F. (54° C.) or below at least about 120° F. (49° C.) and downto ambient temperatures. Methods may comprise providing instructions tomaintain the hermetically sealed vessel at ambient pressure. Methods maycomprise providing instructions to refrain from increasing temperatureby more than 10° C., for example, by more than 7° C. or by more than 5°C.

In some embodiments, methods may further comprise providing instructionsto unseal the vessel and rinse the virgin ion exchange resin materialwith deoxygenated water, for example, prior to use. The virgin ionexchange resin material may be rinsed with deoxygenated water having anyconcentration of dissolved oxygen, dissolved gases, or oxidizingcontaminants as previously described herein. The methods disclosedherein may comprise instructions to rinse the virgin ion exchange resinmaterial immediately prior to use. In some embodiments, the methods maycomprise providing instructions to rinse the virgin ion exchange resinmaterial immediately prior to use while the ion exchange resin is stillcontained within the vessel. For example, the methods may includeproviding instructions to fill the vessel with deoxygenated water andremove interstitial water from the vessel, thus rinsing the virgin ionexchange resin material. Methods may comprise providing instructions tounseal the vessel and rinse the virgin ion exchange resin material priorto use in, for example, water treatment.

In some embodiments, the method of facilitating water treatment maycomprise instructions to return the vessel after removal of the ionexchange resin material. Such instructions may reduce waste of thevessel and reduce operator time.

In accordance with another aspect, there is provided a vessel comprisingvirgin ion exchange resin material and deoxygenated water. In someembodiments, the vessel may be hermetically sealed. The vessel maycomprise an opening with a hermetic seal. The vessel may furthercomprise an inlet and an outlet. The inlet and outlet may comprise ahermetic seal. The inlet may be connected to a source of ion exchangeresin material or a source of deoxygenated water. The outlet may beconnected to a drain for deoxygenated water or a point of use for theion exchange resin material. For instance, the outlet may be connectedto a hose configured to deliver the ion exchange resin material to apoint of use.

The vessel may be a container, tank, barrel, basin, chamber, orreceptacle configured to hold ion exchange resin and deoxygenated water.The vessel may generally have a volume of between about 20 cubic feet(0.57 m³) and about 50 cubic feet (1.42 m³). For example, the vessel mayhave a volume of about 20 cubic feet (0.57 m³), 25 cubic feet (0.71 m³),30 cubic feet (0.85 m³), 35 cubic feet (1.0 m³), 40 cubic feet (1.13m³), 45 cubic feet (1.27 m³), or 50 cubic feet (1.42 m³). The vessel maygenerally have a volume that is capable of observing overheadrestrictions associated with a site in need of ion exchange resinmaterial.

In some embodiments, the vessel may be constructed from a gasimpermeable material. The vessel may be constructed from a material witha high flash point. For instance, the vessel may be constructed from orlined with at least one of stainless steel and epoxy-lined carbon steel.The vessel may be constructed from or lined with polyethyleneterephthalate. Conventionally, ion exchange resin storage andtransportation vessels may be constructed from fiber, plastic, or wood.Such materials, although relatively inexpensive, are not gas impermeableand may contribute to oxidative degradation of ion exchange resinmaterial within the vessel. Furthermore, conventional materials may havea low flash point, which may be unsafe and/or undesirable at certainsites in need of ion exchange resin material.

The vessel may comprise one or more compartments. In accordance withcertain embodiments, the vessel may comprise a liquid impermeablecompartment. The virgin ion exchange resin and deoxygenated water may bepackaged in the liquid impermeable compartment. The liquid impermeablecompartment may comprise substantially no headspace or interstitialspace between the resin beads and water content. In some embodiments,the liquid impermeable compartment may comprise between about 40% andabout 50% moisture content in the form of deoxygenated water. In someembodiments, the liquid impermeable compartment may also be gasimpermeable. The liquid impermeable compartment may be constructed fromthe gas impermeable materials described above. Alternatively, the liquidimpermeable compartment may be constructed from a polymeric material ora metal material which is liquid impermeable.

In some embodiments, the one or more compartments are integral to thevessel. In other embodiments, the one or more compartments are removablefrom the vessel. For instance, the liquid impermeable compartmentcontaining the ion exchange resin may be an ion exchange resin packagingwhich is removable from the vessel.

In some embodiments, the vessel may comprise deoxygenated water havingany concentration of dissolved oxygen, dissolved gases, or oxidizingcontaminants as previously described herein. In some embodiments, thevessel may comprise an interstitial volume of deoxygenated water. Insome embodiments, the vessel may comprise deoxygenated water as residualmoisture, for example, as moisture content previously described herein.

The vessel or a compartment thereof may comprise a predetermined volumeof void space, for example, the vessel or compartment may compriseinterstitial void space between ion exchange resin beads and/or aheadspace. In some embodiments, the void space is limited. The vessel orcompartment may comprise substantially no headspace and/or limitedinterstitial space between resin beads. Limiting the void space maycontribute to stability of the ion exchange resin stored, handled, ortransported within the vessel.

In some embodiments, the vessel may comprise a preservative. The vesselmay comprise a packaged desiccant media. For example, the vessel maycomprise a packaged desiccant media contained within the vessel. Thepackaged desiccant media may be configured to remove oxygen from a voidspace within the vessel. In some embodiments, the desiccant/deoxidantmedia is packaged in a fibrous pillow with a porous design that iscapable of allowing oxygen exchange.

The preservative or desiccant/deoxidant media may be an oxygenscavenging material. The vessel may comprise an oxygen scavengingmaterial. The oxygen scavenging material may capable of removing ordecreasing the level of oxygen within the hermetically sealed vessel. Insome embodiments, the oxygen scavenging material may be in the form ofan oxygen sequestering compound. For example, the oxygen scavengingmaterial may be an oxidative compound. In some embodiments, the oxygenscavenging material comprises a ferrous compound, catechol, ascorbate,ascorbic acid, sodium hydrogen carbonate, citrus extract, an oxidativeenzyme, an unsaturated hydrocarbon, a polyamide, or combinationsthereof. The oxygen scavenging material may further include a catalystto assist in oxidation. For example, the oxygen scavenging material mayinclude a metal halide catalyst. The oxygen scavenging material mayinclude sodium chloride or palladium.

The oxygen scavenging material may be packaged in a gas permeablecontainer. The gas permeable container may be water permeable orimpermeable. The gas permeable container may comprise a gas permeablesachet, a perforated container, a fabric container, a cardboard or papercontainer, or a polymer container. In other embodiments, the oxygenscavenging material may be part of a packaging film or structure. Forinstance, the oxygen scavenging material may line or be part of a vesselstructure. The gas permeable container may be attached to the liquidimpermeable compartment holding the ion exchange resin. In someembodiments, the gas permeable container may be contained on a layeredstrip around the liquid impermeable compartment. In some embodiments, aportion of the liquid impermeable compartment may be removable to exposethe oxygen scavenging material.

The vessel may comprise an indicator of oxygen contamination. In someembodiments, the indicator may comprise a redox indicator in atransparent packaging. The redox indicator may be a first color when ina reduced form. Upon exposure to a predetermined concentration of anoxidant, for example, oxygen, the redox indicator may oxidize and turn asecond color. Thus, the redox indicator may provide a visual indicationof oxygen contamination within the vessel. The indicator of oxygencontamination may be positioned such that it reacts with potentialoxidants inside the vessel but is visible from the exterior of thevessel, for example, through a window. Thus, the indicator may bevisible without opening the hermetic seal of the vessel.

The indicator of oxygen contamination may have a redox midpointpotential E⁰ between about −0.05 V and about +0.06 V at pH 7 and 25° C.For instance, the indicator of oxygen contamination may have a redoxmidpoint potential E⁰ between about −0.05 V and about −0.04 V, betweenabout −0.02 V and about +0.02 V, or between about +0.05 V and +0.06 V atpH 7 and 25° C. The indicator of oxygen contamination may comprise, forexample, indigo tetrasulfonic acid, methylene blue, or thionine.

The preservative, oxygen scavenging material, or indicator of oxygencontamination may be independently or jointly positioned in a designatedcompartment within the vessel. In some embodiments, the preservative,oxygen scavenging material, or indicator of oxygen contamination may bepositioned within the gas impermeable vessel but outside the liquidimpermeable compartment which holds the ion exchange resin anddeoxygenated water. In general, the preservative, oxygen scavengingmaterial, or indicator of oxygen contamination may be positioned suchthat they do not come into direct contact with moisture. Thus, in someembodiments, the preservative, oxygen scavenging material, or indicatorof oxygen contamination may be positioned between an exterior wall ofthe liquid impermeable compartment which holds the ion exchange resinand deoxygenated water and an interior wall of the gas impermeablevessel.

In some embodiments, the virgin ion exchange resin material may becation exchange resin. In some embodiments, the virgin ion exchangeresin material may be anion exchange resin. In yet other embodiments,the virgin ion exchange resin material may be mixed cation exchangeresin and anion exchange resin. The conditions of storage for thevessel, for example temperature, pressure, and/or concentration ofdissolved gases in the deoxygenated water, may vary depending on thetype of ion exchange resin contained within the vessel. For example, ingeneral continuous exposure of anion resins to greater than about 0.05ppm free chlorine should be avoided. At a feed temperature of betweenabout 5° C. and about 10° C., standard crosslinked anion resin may beable to withstand free chlorine levels up to about 0.3 ppm, highlycrosslinked anion resin may be able to withstand free chlorine levels upto about 0.5 ppm, and macroporous anion resin may be able to withstandfree chlorine levels up to about 1 ppm. At a feed temperature of betweenabout 20° C. and about 30° C., standard crosslinked anion resin may beable to withstand free chlorine levels only less than 0.1 ppm, highlycrosslinked anion resin may be able to withstand free chlorine levels upto about 0.1 ppm, and macroporous anion resin may be able to withstandfree chlorine levels up to about 0.5 ppm. Some cation exchange resin,for example, the DIAION® SK1B resin available from the MitsubishiChemical Corporation may have a free chlorine tolerance of about 0.6mg/L at temperatures between about 5° C. and about 10° C. and a freechlorine tolerance of about 0.1 mg/L at temperatures between about 20°C. and about 25° C. The presence of catalysis, for example, iron orcopper may reduce the oxidant levels to which the resins may be exposedwithout significant degradation.

In accordance with another aspect there is provided a system comprisinga vessel including virgin ion exchange resin material and deoxygenatedwater. The vessel may be gas impermeable and capable of beinghermetically sealed, as previously described. The vessel may beconnected or connectable downstream from a source of deoxygenated water.The vessel may be connected or connectable downstream from a source ofion exchange resin material. In some embodiments, the vessel isconnected or connectable upstream from a drain for used deoxygenatedwater. The vessel may be connected or connectable upstream from a pointof use for the virgin ion exchange resin material, for example, via ahose.

In some embodiments, the system comprises an oxygen monitor. The oxygenmonitor may be connected to the vessel and configured to measure aconcentration of oxygen within the vessel. The system may comprise adegasifier, for example an in-line degasifier. The degasifier may be adeoxygenation membrane. For example, the deoxygenation membrane may beprovided by Liqui-Cel® Membrane Contactors (3M Industrial Group,Maplewood, Minn.). The degasifier may be a vacuum degasifier. Thedegasifier may be a column or other device containing an oxygenscavenging resin. The oxygen scavenging resin may include an oxygenscavenging material as previously described. In some embodiments, theoxygen scavenging resin may include a catalyst. The catalyst may includea metal halide. In some embodiments, the catalyst may include sodiumchloride. The catalyst may include palladium or a palladium compound,for example, palladium chloride. The degasifier may be fluidly connectedor connectable upstream from the vessel. The degasifier may be fluidlyconnected or connectable downstream from a source of non-deoxygenatedwater and configured to deoxygenate the non-deoxygenated water.

The system may further comprise a sensor or monitor, for example, apressure sensor or thermometer. The sensor and/or monitor may bepositioned upstream from the vessel and configured to measuretemperature, pressure, pH, conductivity, and/or composition ofdeoxygenated or non-deoxygenated water. The sensor and/or monitor may beelectrically connected to a control module. The control module may beconfigured to control one or more parameter of the in-line degasifierresponsive to a measurement received from the sensor and/or monitor. Thecontrol module may be connected to the oxygen monitor. The controlmodule may be configured to control one or more parameter of the in-linedegasifier responsive to a measurement received from the oxygen monitor.

As shown in FIG. 1, the vessel 100 may comprise virgin ion exchangeresin material and deoxygenated water. The vessel 100 may have anopening 110, an inlet 120, and an outlet 130. The opening, inlet, and/oroutlet may be capable of being hermetically sealed. The inlet may beconnectable to a source of deoxygenated water 140 or a source of ionexchange resin material 150. The outlet may be connectable to a drain160 or a point of use for the ion exchange resin material 170.

As shown in FIG. 2, the system 200 may comprise a vessel 100, having anopening 110, an inlet 120, and an outlet 130. The system may furthercomprise an oxygen monitor 210, a degasifier 220, a sensor or monitor230, and a control module 240.

As shown in FIG. 3, the vessel 100 may have a compartment 105 configuredto hold the virgin ion exchange resin material and deoxygenated water. Acontainer 180 holding a preservative or oxygen scavenging material maybe positioned in the interstitial space exterior to the compartment 105.An indicator of oxygen contamination 190 may be viewable through aviewing window 195 of the vessel 100. The vessel of FIG. 3 may have aninlet and outlet (not shown) in in fluid communication with thecontainer 180. For example, the vessel may contain an inlet or outlet influid communication with the liquid impermeable container which holdsthe ion exchange resin and deoxygenated water.

EXAMPLES Example 1: Application of the Gas Impermeable Vessel ComprisingCation Resin

In one exemplary application, a cation exchange resin that is used in adelithiating application has had issues with sulfates leaching from theresin prior to being used. Conventionally, the resin is rinsed beforebeing put online and the rinse water is drained to a hot well which isradioactive. The radioactive hot well has limitations on the volume ofrinse water that it can accept. Furthermore, it is expensive to treatradioactive water from the hot well.

The usage of a gas impermeable vessel comprising ion exchange resinmaterial and deoxygenated water may allow the ion exchange resin to berinsed prior to use in a non-hot area of the plant, for example, wherethere are no restrictions on the amount of rinse water generated. Therinse water can go to a common drain and the resin could then betransported to vessels in a radioactive area by hoses.

Example 2: Stability of Stored Virgin Ion Exchange Resin Material

Experiments were performed to test whether various methods would lessenor prevent degradation of the ion exchange resin. After treating the ionexchange resins and storing them for a specified period, the resins weretested for degradation. Organic sulfate compound (SO₄) concentration wasmeasured by UV light adsorption to determine degree of degradation ofthe resin. The results are presented in Table 1.

The experimental lots (E) were rinsed with deoxygenated water andpackaged in a gas impermeable vessel with an oxygen scavenging sachet,as described above. The comparison lots (C) were processed and stored byvarious conventional methods.

TABLE 1 Degradation of Ion Exchange Resin in Storage Measured asIncrease in Organic Sulfate Days Initial SO₄ Final SO₄ SO₄ Increase Lot# Stored Rinse (ppm) Rinse (ppm) Rate E1 90 0.166 0.1 0 E2 180 0.1660.212 0.00026 C1 11 0.007 0.639 0.057 C2 204 0.989 6.96 0.029 C3 1010.285 3.78 0.035 C4 N/A Not tested 8.42 N/A C5 101 0.163 4.05 0.038 C614 0.022 0.109 0.006 C7 14 0.013 0.087 0.005 C8 14 0.008 0.156 0.0106 C914 0.02 0.308 0.0206 C10 14 0.007 0.368 0.026 C11 14 0.044 1.07 0.073C12 14 0.004 0.727 0.052 C13 14 0.024 0.52 0.035 C14 14 0.007 0.151 0.01C15 69 0.035 24.52 0.355

The results show a decrease in rate of degradation when treating andstoring the ion exchange resins by the methods disclosed herein. Theexperimental samples had a significantly lower SO₄ increase rate thanthe measured comparison samples. Thus, the experimental samples werefound to be 20 to 1500 times more stable, when measured as compared tothe conventional ion exchange resin samples. Accordingly, the methodsdisclosed herein provide increased stability for ion exchange resinafter storage for an extended period of time.

Example 3: Effect of Temperature on Stored Virgin Ion Exchange ResinMaterial

Experiments were performed to test the rate of degradation of the ionexchange resins with increasing temperature. Ion exchange resin wastested by measuring total organic carbon (TOC) after heating in 500 mLof water for one week while bubbling air through the solution. Table 2shows the comparable amount of degradation for ion exchange resinmaintained at room temperature.

TABLE 2 Comparative Degradation of Ion Exchange Resin with IncreasedTemperature Test Heating Temperature Comparative Degradation for 1 week(° C.) at 20° C. (time) 20  1 week 30  2 weeks 40  4 weeks 50  8 weeks60 16 weeks 70 32 weeks 80 64 weeks

Every 10° C. increase in temperature resulted in a two-fold increase inrate of degradation as compared to holding the ion exchange resin inroom temperature for the same amount of time. Thus, temperature appearsto have an adverse effect on rate of degradation of ion exchange resin.Accordingly, degradation may be lessened or prevented by refraining fromincreasing temperature by more than 10° C., as disclosed herein.

The phraseology and terminology used herein is for the purpose ofdescription and should not be regarded as limiting. As used herein, theterm “plurality” refers to two or more items or components. The terms“comprising,” “including,” “carrying,” “having,” “containing,” and“involving,” whether in the written description or the claims and thelike, are open-ended terms, i.e., to mean “including but not limitedto.” Thus, the use of such terms is meant to encompass the items listedthereafter, and equivalents thereof, as well as additional items. Onlythe transitional phrases “consisting of” and “consisting essentiallyof,” are closed or semi-closed transitional phrases, respectively, withrespect to the claims. Use of ordinal terms such as “first,” “second,”“third,” and the like in the claims to modify a claim element does notby itself connote any priority, precedence, or order of one claimelement over another or the temporal order in which acts of a method areperformed, but are used merely as labels to distinguish one claimelement having a certain name from another element having a same name(but for use of the ordinal term) to distinguish the claim elements.

Those skilled in the art should appreciate that the parameters andconfigurations described herein are exemplary and that actual parametersand/or configurations will depend on the specific application in whichthe disclosed methods and materials are used. Those skilled in the artshould also recognize or be able to ascertain, using no more thanroutine experimentation, equivalents to the specific embodimentsdisclosed. For example, those skilled in the art may recognize that themethod, and components thereof, according to the present disclosure mayfurther comprise a network or systems containing ion exchange resins orgas impermeable vessels disclosed herein. It is therefore to beunderstood that the embodiments described herein are presented by way ofexample only and that, within the scope of the appended claims andequivalents thereto; the disclosed embodiments may be practicedotherwise than as specifically described. The present systems andmethods are directed to each individual feature, system, or methoddescribed herein. In addition, any combination of two or more suchfeatures, systems, or methods, if such features, systems, or methods arenot mutually inconsistent, is included within the scope of the presentdisclosure. The steps of the methods disclosed herein may be performedin the order illustrated or in alternate orders and the methods mayinclude additional or alternative acts or may be performed with one ormore of the illustrated acts omitted.

Further, it is to be appreciated that various alterations,modifications, and improvements will readily occur to those skilled inthe art. Such alterations, modifications, and improvements are intendedto be part of this disclosure, and are intended to be within the spiritand scope of the disclosure. In other instances, an existing facilitymay be modified to utilize or incorporate any one or more aspects of themethods and systems described herein. Thus, in some instances, thesystems may involve connecting or configuring an existing facility toperform a method of reducing a rate of oxidative degradation of an ionexchange resin, or to house or utilize an ion exchange resin or gasimpermeable vessel, as described herein. Accordingly the foregoingdescription and figures are by way of example only. Further thedepictions in the figures do not limit the disclosures to theparticularly illustrated representations.

While exemplary embodiments of the disclosure have been disclosed, manymodifications, additions, and deletions may be made therein withoutdeparting from the spirit and scope of the disclosure and itsequivalents, as set forth in the following claims.

What is claimed is:
 1. A method of stabilizing virgin ion exchange resinmaterial, the method comprising: rinsing the virgin ion exchange resinmaterial with deoxygenated water to produce a rinsed virgin ion exchangeresin material; introducing the rinsed virgin ion exchange resinmaterial into a liquid impermeable compartment of a gas impermeablevessel; and hermetically sealing the vessel.
 2. The method of claim 1,further comprising introducing an oxygen scavenging material into thegas impermeable vessel.
 3. The method of claim 2, comprising positioningthe oxygen scavenging material between an exterior wall of the liquidimpermeable compartment and an interior wall of the gas impermeablevessel.
 4. The method of claim 1, comprising introducing the rinsedvirgin ion exchange resin material into the gas impermeable vesselcomprising at least one of polyethylene terephthalate, stainless steel,and epoxy-lined carbon steel.
 5. The method of claim 1, comprisingrinsing the virgin ion exchange resin material with deoxygenated waterhaving a concentration of dissolved oxygen of less than about 10 ppb. 6.The method of claim 5, comprising rinsing the virgin ion exchange resinmaterial in the gas impermeable vessel.
 7. A method of stabilizingvirgin ion exchange resin material, the method comprising: rinsing thevirgin ion exchange resin material with deoxygenated water to produce arinsed virgin ion exchange resin material; introducing the rinsed virginion exchange resin material into a gas impermeable vessel; introducingan oxygen scavenging material into the gas impermeable vessel, theoxygen scavenging material being positioned such that it does not comeinto direct contact with moisture; and hermetically sealing the vessel.8. The method of claim 7, further comprising introducing the rinsedvirgin ion exchange resin material into a liquid impermeable compartmentof the gas impermeable vessel.
 9. The method of claim 8, comprisingpositioning the oxygen scavenging material between an exterior wall ofthe liquid impermeable compartment and an interior wall of the gasimpermeable vessel.
 10. The method of claim 7, wherein introducing theoxygen scavenging material comprises introducing a material comprising aferrous compound, catechol, ascorbate, ascorbic acid, sodium hydrogencarbonate, citrus extract, an oxidative enzyme, an unsaturatedhydrocarbon, a polyamide, or combinations thereof.
 11. The method ofclaim 7, further comprising introducing an indicator of oxygencontamination.
 12. The method of claim 11, wherein introducing theindicator of oxygen contamination comprises introducing a visualindicator having a redox midpoint potential E⁰ between about −0.05 V andabout +0.06 V at pH 7 and 25° C.
 13. A method of facilitating watertreatment at a site in need thereof, the method comprising: providing arinsed virgin ion exchange resin material in deoxygenated water, therinsed virgin ion exchange resin material positioned in a liquidimpermeable compartment of a hermetically sealed gas impermeable vessel.14. The method of claim 13, comprising providing the oxygen scavengingmaterial positioned between an exterior wall of the liquid impermeablecompartment and an interior wall of the gas impermeable vessel.
 15. Themethod of claim 13, comprising providing the deoxygenated water in anamount between about 40% and about 50% of the virgin ion exchange resinmaterial.
 16. The method of claim 13, comprising providing thedeoxygenated water having less than about 10 ppb dissolved oxygen. 17.The method of claim 13, further comprising providing an indicator ofoxygen contamination in the gas impermeable vessel.
 18. A hermeticallysealed vessel comprising virgin ion exchange resin material indeoxygenated water having less than about 10 ppb dissolved oxygen, andan oxygen scavenging material.
 19. The vessel of claim 18, wherein thevirgin ion exchange resin material in the deoxygenated water ispositioned in a liquid impermeable compartment of the hermeticallysealed vessel.
 20. The vessel of claim 19, wherein the oxygen scavengingmaterial is positioned between an exterior wall of the liquidimpermeable compartment and an interior wall of the vessel.
 21. Thevessel of claim 18, wherein the oxygen scavenging material comprises aferrous compound, catechol, ascorbate, ascorbic acid, sodium hydrogencarbonate, citrus extract, an oxidative enzyme, an unsaturatedhydrocarbon, a polyamide, or combinations thereof.
 22. The vessel ofclaim 18, being constructed from a material comprising at least one ofpolyethylene terephthalate, stainless steel, and epoxy-lined carbonsteel.
 23. The vessel of claim 18, further comprising an indicator ofoxygen contamination.